Unlocking Catalysis Using Oxidatively Induced Reductive Elimination.

Oxidatively induced reductive elimination (OIRE) has become a crucial chemical process to enable the effective formation of otherwise much less accessible products. The chemically, electrochemically, or photochemically triggered oxidation of appropriate metal complexes leading to a reductive elimination process otherwise chemically unfavorable has long been studied in stoichiometric metal-centered reactions. However, its conscious inclusion and targeted application in catalysis is a rather recent development. Ruthenium and Group 9 metal complexes are particularly representative examples of how the observed OIRE abilities can be modulated using different coupling partners. Parallels can be drawn between rhodium and iridium, which have a long history as efficient catalysts, and their more readily available 3d row metal neighbor, i. e. cobalt, with ruthenium also providing a matching reactivity. This review explores the history of OIRE reactions throughout the last few centuries, highlighting the role of Ti, Mo, Fe, Hg, Ni, Ru and group 9 transition metals as key players in C-H bond functionalization and OIRE chemistry, discussing the most relevant studies published in the field whilst pinpointing research gaps that require new theoretical and mechanistic studies, with the final goal of unlocking the full potential of OIRE chemistry in organometallic homogeneous catalysis.